The present invention relates to a cosmetic resin composition consisting essentially of amphoteric urethane resin and a cosmetic using such a resin composition, and particularly, to a cosmetic resin composition used for a skin care product a hair care product and the like as a hair fixative, a film forming agent, a conditioning agent, a viscosity controlling agent and the like, and a cosmetic using the same.
Conventionally, a cationic acrylic resin, an anionic acrylic resin, an amphoteric or an ionic/cationic acrylic resin, a nonionic polyvinyl pyrrolidone resin and the like are used as a base resin of a hair fixative. When such a resin is used as a base resin, hair is set stiff, resulting in a good setting property (stiffness), but feel and combability are inferior and also flaking may occur. On the other hand, when feel and combability come first, not only setting property becomes insufficient, but also problems such as stickiness and the like may occur. Thus, it is difficult for the conventional base resin to satisfy all properties required for a hair fixative, such as stiffness, feel, combability and anti-flaking property.
Then, an application of an anionic urethane resin as a base resin for a hair fixative is proposed as seen in Japanese Provisional Publication TOKKAIHEI 6-321741. When such an anionic urethane resin is used, a hair fixative having good stiffness, feel and anti-flaking property, which are inconsistent to each other, can be prepared. In this viewpoint, a hair fixative using such an anionic urethane resin is superior to a hair fixative using the above mentioned acrylic resin. However, when the anionic urethane resin is used, a problem of inferior shampoo removability may be caused.
Accordingly, it is an object of the present invention to provide a cosmetic resin composition for preparation of a hair fixative having all the properties of stiffness, shampoo removability, feel, gloss, combability and anti-flaking property and to provide a cosmetic using such a cosmetic resin composition.
In accordance with a first aspect of the present invention to achieve the object described above, there is provided a cosmetic resin composition consisting essentially of an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule thereof, the amphoteric urethane resin having polysiloxane linkage in its structure. In accordance with a second aspect of the present invention, there is provided cosmetics using the cosmetic resin composition.
The inventors of the present invention found that a hair fixative having stiffness, feel, combability, anti-flaking property and the like can be obtained by using an amphoteric urethane resin having a carboxyl group and a tertiary amino group in one molecule thereof as a base resin and filed a patent application about a resin composition consisting essentially of the amphoteric urethane resin Japanese Patent Application No. TOKUGANHEI 10-27595). Improvement in each property when using the amphoteric resin is due to the following reason. That is, using the urethane resin as a main skeleton of a base resin makes it possible that stiffness is compatible with feel, combability and anti-flaking property, which are originally contrary to each other, due to elasticity and toughness of the urethane resin. Further, by using the amphoteric urethane resin having a carboxyl group and a tertiary amino group, it becomes possible to prepare a hair fixative superior in waterproof against neutral water because the carboxyl group and the tertiary amino group are ion-bonded, and also superior in shampoo removability because the ion-bond is cut by shampoo. In addition, since the amphoteric urethane resin has a cationic tertiary amino group, which interacts with a negatively charged hair surface, in its molecular chains, better adhesion can be obtained compared with a conventional anionic urethane resin.
Thus, in the case where the amphoteric urethane resin is used as a base resin, shampoo removability can be improved compared with the case where the conventional anionic urethane resin is used. However, to obtain sufficient shampoo removability, there are compositional restrictions, to some degree, such as adjustment of molecular weight of the amphoteric urethane resin, choice of urethane skeleton or the like, which may be a defect of low degree of freedom in designing physical properties, such as hardness, flexibility or the like, important for polymer to be used for a hair fixative. Then, the inventors further made researches about the resin composition consisting essentially of the amphoteric urethane resin. As a result, it was found that further improvement in shampoo removability can be obtained by the amphoteric urethane resin even with a higher molecular weight or a low glass transition temperature by introducing a structural unit derived from an ethylene oxide in the structure of the amphoteric urethane resin as nonionic hydrophilic component, and hardness and elasticity of the base resin which contribute to feel or stiffness required for a hair fixative, can be widely controlled. Thus, the inventors have attained the present invention.
The present invention will hereinafter be described by way of embodiments thereof.
The cosmetic resin composition of the present invention consists essentially of an amphoteric resin having a carboxyl group and a tertiary amino group in one molecule thereof. The most characteristic point of the present invention is that the amphoteric urethane resin has a structural unit derived from an ethylene oxide in its structure. In addition, the phrase xe2x80x9cconsisting essentially of an amphoteric urethane resinxe2x80x9d means generally preparation of the cosmetic resin composition of interest by adding other components into the amphoteric urethane resin, however, includes the case where the cosmetic resin composition consists only of the amphoteric urethane resin.
The above-mentioned amphoteric urethane resin having a structural unit derived from an ethylene oxide may be obtained, for example, by reacting a polyol compound [component (A)], a polyisocyanate compound [component (B)], a polyethylene oxide derivative [component (C)] having an active hydrogen and a compound [component (D)] having an active hydrogen and a carboxyl group with each other in excess of isocyanate groups so as to produce a prepolymer containing an isocyanate group and reacting the prepolymer with a compound [component (E)] having an active hydrogen and a tertiary amino group. Alternatively, the amphoteric urethane resin having a structural unit derived from an ethylene oxide may be obtained by changing the reaction order of the component (D) for the component (E) in excess of isocyanate groups so as to produce a prepolymer containing an isocyanate group and reacting the prepolymer with the component (D). The amphoteric urethane resin of interest can be produced more easily and more safely by such methods than the conventional method. In addition, if both the component (D) and the component (E) are simultaneously reacted together with the components (A) to (C) In the above methods, a carboxyl group of the component (D) and a tertiary amino group of the component (E) initially form a salt which becomes insoluble to the reaction system and a reaction with the isocyanate compound may not occur even in the presence of an OH group. As a result, the amphoteric urethane resin of interest cannot be produced. That is, as above mentioned, the amphoteric urethane resin having a structural unit derived from an ethylene oxide can be produced by firstly reacting one of the component (D) and the component (E) together with the components (A) to (C) and then reacting the other component (D) or (E).
The polyol compound of the component (A) is not specifically limited, but any of the polyol compounds generally used for producing polyurethane. Examples of the polyol compound include polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, polyolefin polyol, polyacrylic ester polyol. These may be used either alone or in combination thereof. Among all, polyester polyol and polyether polyol are especially preferred. Examples of the polyester polyol include products obtained by condensation polymerizing at least one of dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid and the like with at least one of polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, spiroglycol, trimethylolpropane and thelike, and products obtained by ring-opening addition polymerizing cyclic ethers such as ethylene oxide, propylene oxide oxetane and tetrahydrofuran into water, polyol, phenols such as bisphenol A, hydrogenated phenols, primary amines and secondary amines. Examples of such products include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol and products (either a blocked copolymer or a random copolymer in case of a copolymer) obtained by ring-opening polymerizing lactones. Further, examples of polyether polyol may be obtained by ring-opening addition polymerizing cyclic ethers such as ethylene oxide, propylene oxide oxetane and tetrahydrofuran into water, polyhydric alcohols for synthesizing the polyester polyol, phenols such as bisphenol A, hydrogenated phenols, primary amines and secondary amines. Examples of such products include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol and products (either a blocked copolymer or a random copolymer in case of a copolymer) obtained by ring-opening addition polymerizing at least one of propylene oxide and ethylene oxide into bisphenol A.
The polyisocyanate compound of the component (B) is not specifically limited. Examples thereof include organic diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds and aromatic diisocyanate compounds. These may be used either alone or in combination thereof. Examples of the aliphatic diisocyanate compounds include ethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate. Examples of the alicyclic diisocyanate compounds include hydrogenated diphenyl methane-4,4xe2x80x2-diisocyanate, 1,4-cyclohexane diisocyanate methylcyclohexylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate. Examples of the aromatic diisocyanate compounds include diphenyl methane-4,4xe2x80x2-diisocyanate, xylylene diisocyanate, toluene diisocyanate and naphthalene diisocyanate. Among all, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate and the like are preferred in viewpoints of the performance cost.
The specific polyethylene oxide derivative of the component (C) is not specifically limited, but any of compound wherein a structural unit derived from an ethylene oxide (abbreviated to xe2x80x9cEOxe2x80x9d, hereinafter) can be introduced into the structure of the amphoteric urethane resin, may be used. The structural unit derived from the EO introduced into the structure of the amphoteric urethane resin includes an EO unit represented by the following general formula (1) and a propylene oxide (abbreviated to xe2x80x9cPOxe2x80x9d, hereinafter) unit represented by the following general formula (2), among which the EO unit is preferred. The amphoteric urethane resin may have both of the EO unit and the PO unit. The ratio of the EO unit and the PO unit is preferably within a range of EO unit/PO unit=10/0 to 2/8 on a weight basis, more preferably EO unit/PO unit=10/0 to 4/6.
A repetitive number xe2x80x98nxe2x80x99 of the EO unit in the above general formula (1) is preferably within a range of n=3 to 300, more preferably n=20 to 120. When the number xe2x80x98nxe2x80x99 is less than 3, the amount of the EO unit introduced into the amphoteric urethane resin is too small, so that sufficient hydrophilic property cannot be imparted, thereby sufficient shampoo removability may not be obtained. On the other hand, when the number xe2x80x98nxe2x80x99 exceeds 300, the hydrophilic property of the amphoteric urethane resin itself becomes too strong so as to have bad effects on moisture resistance and the like. Also, a repetitive number xe2x80x98mxe2x80x99 of the PO unit in the above general formula (2) is preferably within the same range as the above EO unit. In addition, when having both the EO unit and the PO unit, it is preferred that a total amount of xe2x80x98nxe2x80x99 and xe2x80x98mxe2x80x99 is within the above range. That is, the total amount is within a range of n+m=3 to 300, more preferably n+m=20 to 120.
Examples of the polyethylene oxide derivative [component (C)] include polyoxyethylene glycol (PEG) and polyoxyethylene polyoxypropylene glycol (EOPO blocked copolymer), among which polyoxyethylene glycol is preferred. The above polyethylene oxide derivative [component (C)] may be either of a type having OH groups at both terminals, a type having NH2 groups at both terminals, a type having an OH group at one terminal and a type having an NH2 at one terminal. When the type having OH groups at both terminals is used, the amphoteric urethane resin having the EO unit as a main chain can be obtained. When the type having an OH group at one terminal or the type having an NH2 at one terminal is used, the amphoteric urethane resin having the EO unit as a side chain or at a terminal can be obtained.
The above specific polyethylene oxide derivative [component (C)] has preferably a molecular weight of 200 to 20,000, more preferably 2,000 to 10,000.
The compound [component (D)] having an active hydrogen and a carboxyl group is not specifically limited, but any of compound which may have at least one active hydrogen and at least one carboxyl group in its molecule. Examples include dimethylol propionic acid (DMPA), dimethylol butanoic acid and polycaprolactone diol having a carboxyl group. These may be used either alone or in combination thereof.
The compound [component (E)] having an active hydrogen and a tertiary amino group is not specifically limited, but any of compound which may have at least one active hydrogen and at least one tertiary amino group in its molecule. Examples include N-alklyldialkanolamine compound such as N-methyldiethanol-amine, and dimethylaminoethanol. These may be used either alone or in combination thereof.
In preparation of the prepolymer containing an isocyanate group by using each of the above components, it is preferred to use a chain extender. The use of the chain extender makes it possible to adjust various properties of the obtained amphoteric urethane resin as a final product. The chain extender is not specifically limited. Examples include low molecular weight polyols and amines.
In preparation of the amphoteric urethane resin, solvents may be used, as required. For example, it is especially preferred to use solvents which may solve both a raw material and the obtained polyurethane. Examples include amides such as N-methyl pyrrolidone, dimethylformamide and dimethylacetamide, ketones such as acetone and methyl ethyl ketone and esters such as ethyl acetate as well as cellosolve acetate and cellosolve ether. In addition, in preparation of the amphoteric urethane resin, a polymerization catalyst conventionally known in the field of polyurethane may be used. Examples include tertiary amine catalyst and organometallic catalyst. As the tertiary amine catalyst, [2,2,21] diazabicyclo octane (DABCO), tetramethylene diamine, N-methylmorpholine, diazbicyclo undecene (DBU) may be used. As the organometallic catalyst, examples include dibutyltindilaurate.
It is preferred that the ratio of the carboxyl group and the tertiary amino group (the ratio of the numbers of both groups) in the amphoteric urethane resin obtained by using each of the above components is the carboxilic group/the tertiary group=1/10 to 10/1. That is, when the ratio is within the above range, excellent washability may be imparted.
In addition, any other ingredients generally used in cosmetics other than the specific amphoteric urethane resin, such as pigment, coloring matter, colorant, fragrance, surfactant, moisturizer, preservative, antiseptic, disinfectant and antioxidant may be added to the cosmetic resin composition.
The cosmetic resin composition of the present invention is used for, for example, hair fixatives such as a mousse hair fixative, a gel hair fixative, a spray hair fixative and a pump spray hair fixative, a conditioning shaving cream agent, a film forming agent such as skin care lotion, foundation, eye liner and manicure, and viscosity adjuster. Especially, the cosmetic resin composition is useful for a hair fixative.
It is preferred that the specific amphoteric urethane resin is applied for the above usage after being dispersed as a dispersion by dispersing thereof into water or being solubilized as an aqueous solution by solubilizing thereof into water, respectively. In this case, it is preferred that the amphoteric urethane resin is dispersed into water containing aliphatic polyamine. That is, when the polymer is reacted with the aliphatic polyamine as the polymer is dispersed into water by controlling polymerization in excess of isocyanate groups, NH groups and NH2 groups of the aliphatic polyamide rapidly react with the isocyanate groups to generate urea bonds in water, resulting in acceleration of polymerization. The aliphatic polyamine is not specifically limited. Examples include triethylamine, ethylene diamine, propylene diamine, piperazine and diethlylene triamine. Further, it is possible that silane coupling agent may be added into the dispersion of the amphoteric urethane resin for improvement of adhesive property with other base materials. Still further, various additives such as a protective colloid agent, an antibacterial agent and an antifungal agent may be added to give preservation stability.